Heterocyclic bis acetones, thioacetones, and selenoacetones



Patented Aug. 29,

UNITED STATES PATENT OFFICE HETERUCYCLKC BIS ACETONES, THIOACE- TONES,AND SELENOACETONES Leslie G. S. Brooker and Frank L. White, Rochester,N. 25., assignors to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No Drawing. Application September 4, 1948,Serial No. 47,948

20 Claims.

wherein R and R1 each represents an alkyl group (i. e., an alcoholradical), e. g., methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl,isoamyl, shydroxyethyl, 'y-hydroxypropyl, ,B-methoxyethyl,(B-ethoxyethyl, 'allyl, Z-methallyl, benzyl (phenylmethyl),,e-phenylethyl, fi-carboxyethyl, carboxymethyl, a-carboxyethyl,/-carboxypropyl, {3-- acetoxyethyl, 'y-acetoxypropyl,carbomethoxymethyl, carbethoxymethyl, B-carbomethoxyethyl,e-carhethoxyethyl, phenoxymethyl, B- phenoxyethyl,fi-phenylmeroaptoethyl, phenylmercaptomethyl, etc., d and n eachrepresents a positive integer of from 1 to 2, R2 and R3 each representsa hydrogen atom or an alkyl group (i. e., an alcohol radical), e. g.,methyl, ethyl, etc., Q represents an atom selected from the groupconsisting of an oxygen atom, a sulfur atom and a selenium atom, Z andZ1 represents the non-metallic atoms necessary to complete aheterocyclic nucleus containing from 5 to 6 atoms in the heterocyclicring, R, in addition represents an aryl group when Z represents thenon-metallic atoms necessary to complete a hetero-cyclic nucleus of thethiazole series, the benzothiazole series, the thiazoline series or the3,3- dialkylindolenine series, and R1 in addition represents an arylgroup when Z1 represents the nonmetallic atoms necessary to complete aheterocyclic nucleus of the thiazole series, the hemethiazole series,the thiazoline series or the 3,3- dialkylindolenine series. Morespecifically, Z and Z1 each represents the non-metallic atoms necessaryto complete a heterocyclic nucleus of the oxazole series (e. g., methyl,l-phenyloxazole, 4- ethyloxazole, 4,5-diphenyloxazole, 5-pheny1oxazole),the benzoxazole series (e. g., henzoxazcle, 5-ch1orobenzoxazole,.B-phenylbenzoxazole, 5- methylbenzoxazcle, 5-hydroxybenzoxazole, 5-methoxybenzoxazole, etc.), the naphthoxazole series (e. g.,a-n'aphthoxazole, fi-naphthoxazole, etc.) the thiazole series (e. g.,thiazole, -methyh thiazole, -phenylthiazole, 4,5-dipheny1thiazo1e,E-phenylthiazole, 4,5-dimethylthiazole, l-(2-thieny1)thiazole, etc.),the benzothiazole series (e. g., benzothiazole, 4-phenylbenz0thiazole,5- phenylbenzothiazole, l-methylbenzothiazole, 5- methylbenzothiazole,5-methoxybenzothiazole, 5-

ethoxybenzothiazole, G-methylbenzothiazole, 6- methoxybenzothiazole,6-ethoxybenzothiazole, 5- chlorobenzothiazole, 6-chlorobenzothiazole,5,6- dimethoxybenzothiazole, 5,6 dioxymethylenebenzothiazole,tetrahydrobenzothiazole, 5-bromobenzothiazole, 5-iodobenzothiazole,4-ethoxybenzothiazole, etc.), the naphthothiazole series (e. g.,a-naphthothiazole, ,B-naphthothiazole, etc.), the selenazole series(ei-methylselenazole, l-phenylselen'azole, etc.), the benzoselenazoleseries (benzoselenazole, fi-chlorobenzoselenazole,tetrahydrobenzoselenazole, etc.), the thiazoline series (e. g.,thiazoline), the 3,3-dialky1indolenine series (e. g.,3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7trimethylindolenine, etc.), the quinoline series (e. g., quinoline, 6-methylquinoline, 7-methylquinoline, B-methyl quinoline,fi-chloroquinoline, 8-chloroquinoline,

' l-chloroquinoline, 5-ethoxyquinoline, G-ethoxyquinoline,'7-ethoxyquinoline, B-methoxyquinoline, etc.), the pyridine series (e.g., pyridine, 51 methylpyridine, etc.), etc.

The bis acetones formulated above can be prepared, in accordance withour invention, by reacting a metal oxide, a metal hydroxide, a metalsulfide, a metal hydrosulfide, a metal selenide, or a metalhydroselenide, with a carbocyanine selected from those represented bythe following general formula:

wherein R, R1, R2, R3, Z, Z1, d and n have the values set forth above,Q1 represents a sulfur atom or a selenium atom, R4 represents an alkylgroup, e. g. methyl, ethyl, n-propyl, isobutyl, nbutyl, n-hexyl, lauryl,cetyl, etc. (e. g. an alkyl group, especially a primary alkyl group,containing 1 to 20 carbon atoms, and X represents an anion.

If a metal sulfide or hydrosulfide is employed, the resulting compoundis a his thioacetone, regardless of the value of Q1 in the startingcarbocyanine dye (Formula II). If a metal selern'de or hydroselenide isused, the resulting compound is a his selenoacetone regardless of thevalue of Q1 in the starting carbocyanine dye. If a metal oxide orhydroxide is used, the resulting compound is bis acetone regardless ofthe value of Q1 in the starting material.

The reactions are advantageously effected in a diluent. Alcohols, suchas methyl, ethyl, npropyl, isopropyl, n-butyl and tort. butyl areadvantageously employed. Heat accelerates the reaction and temperaturesbetween 50 and 150 C. are advantageously employed, although higher orlower temperatures can be used.

As metal oxides and hydroxides, sulfides and hydrosulfides, selenidesand hydroselenides, the alkali metal compounds, especially sodium andpotassium, are advantageously employed. A1- kaline earth compounds, e.g. calcium, strontium and barium compounds can also be used.

The following examples will serve to illustrate further the manner ofobtaining our new bis acetones, bis thioacetones and bis selenoacetones.

Example 1.-Bzs(3-ethyl-2 (3) -ben2othiazolylidene) thioacetone Asolution of 1.16 g. (l mol.+l%) of sodium sulfide in cc. of water wasadded to a suspension of 4.00 g. (1 mol.) of3,3-diethyl-9-methylmercaptothiacarbocyanine iodide in 75 cc. of ethylalcohol, and the reaction mixture was heated at the refluxingtemperature for minutes. After chilling at 0 C., the product wascollected on a filter and washed with methyl alcohol. The yield ofproduct was 75% crude and 68% after purification (the crude product wasdissolved in hot pyridine and 5 volumes of methyl alcohol was added tothe hot filtrate). The reddish crystals with blue reflex had a meltingpoint of 29l-j292 C. with decomposition, and they sensitized aphotographic gelatino-silverbromoiodide emulsion to about 610 nm withmaxima sensitivity at about 525 and 560 m Example 2.--Bis (3-ethyZ-2 (3)-benzothiazo- Zifllidene) selemoacetone A solution of 3.75 g. (1mol.+200% excess) of sodium selenide in cc. of water was added to asuspension of 5.38 g. (1 mol.) of 3,3'-diethyl-9-methylmercaptothiacarbocyanine iodide in 50 cc. of ethyl alcohol, andthe reaction mixture was heated at the refluxing temperature for 5minutes. After chilling at 0 C., the solids were col lected on a filterand washed with methyl alcohol. The mixed solids were extracted with 70cc. of hot oyclopentanone and the suspension was filtered. To the hotfiltrate was added 280 cc. of ethyl alcohol and the mixture was chilledat 0 C. After another similar purification, the yield was 50%. The greencrystals had a melting point of 269-271 C. with decomposition, and theysen sitized a photographic gelatino-silver-bromoiodide emulsion to about630 m with maximum sensitivity from about 540 m to about 590 mBis(3-ethyl-2 (3) -benzothiazolylidene) acetone, represented by thefollowing formula:

N 412115 zHs was prepared in a manner similar to that described inExample 2 by adding a solution of 3.95

g. (1 mol.+200% excess) of potassium hydroxide in 5 cc. of water to asuspension of 5.38 g. (1 mol.) of3,3-diethyl9-methylmercaptothiacarbocyanine iodide in cc. of ethylalcohol, and heating the reaction mixture at the refluxing temperaturefor 15 minutes.

Example 3.1 [1 ethyl-2 (1) fi-naphthothiazolylz'denel -3 [1 -ethy'l-2(1) -qainolylidenel thicacetone To a suspension of 2.77 g. (1 mol.) of1,3-diethyl-9-methylmercapto-4,5-benzothia2-carbocyanine perchlorate in25 cc. of ethyl alcohol was added 0.78 g. (1 mol.+100%) of sodiumsulfide dissolved in 10 cc. of water, and the reaction mixture washeated at the refluxing temperature for 10 minutes. After chilling, theproduct was collected on a filter and washed with methyl alcohol. It waspurified by being dissolved in hot pyridine, and adding methyl alcoholto the hot filtrate. The yield of product was crude and 36% after twosuch purifications. The dark green needles had a melting point of 242243C. with decomposition, and they sensitized a photographicgelatino-silver-bromiodide emulsion from about 530 m to about 680 m withmaxima sensitivity at about 570 rm. and 640 m Example 4.1-[3-ethyl 2(3)benzothiaeolylidene] -3- [l-ethyZ-G-methoxy 2(1) qaz'nonlylz denelthz'oacetone CzHs To a suspension of 1.07 g. of l,3-diethyl-6'-methoxy-Q-methylmercaptothia-Z"-carbocyanine perchlorate in 25 cc. ofethyl alcohol was added 0.30 g. of sodium sulfide in 5 cc. of water, andthe reaction mixture was heated at the refluxing temperature for 10minutes. After chilling, the product was collected on a filter andwashed with methyl alcohol. It was purified by being dissolved in hotpyridine, and adding methyl alcohol to the hot filtrate. The yield ofproduct was 54% crude, and 36% after two such purifications. The greenneedles with a bronze reflex had a melting point of 23l-233 C. withdecomposition, and they sensitized a photographicgelatino-silver-bromoiodide emulsion from about 530 m to about 670 m,with maxima sensitivity at about 555 mi and about 640 m Example 5 .-Bis3-ethyl-2 3) -a-naphthothiazolylidene) thzoacetone acetate it asus'finsion of 6.16 g. &1 mar. tr sla -db ethyI-Q-methylmercapto 6,7,6)?dibeniothia atbocyanine iodide in 20 co. or ethyl alcohol was added 0,65g. (1 'I'nol;|-l50% excess) of sodium sulfide dissolved in 2 cc. ofwater, and the reaction mixture heated at the refluxing temperature for10 minutes. After chilling, the product was eolle' ted on a filter andwashed with methyl alcohol, It was purified by being dissolved in hotpyridine, and adding methyl alcohol to the hot filtrate. The yield ofproduct was 84% crude, and 25% after we such Durifications. The orangecrystals had a melting point above 300 C., and they sensitized aphotographic gelatino-silverbromoiodide emulsion from about 530 m toabout 610 m Example 6.1-[3-ethyl 2(3) -benzosele1'zazolylz'clenel-3-[3-ethyl 2(3)-benzcthiazolylidenelthz'oaceione Toa sup'en'sion of Tl-.59 g. (1 mol.) of 3,3-diethyl-9methylmercaptoselenathiacarbocyanine iodide-m to cc. of ethyl alcoholwas added 0.16 g. (rmoi.+r uc% exeess) or sodium Sulfide dissolved incc. of water, and the reaction mixture was heated at the refluxingtemperature for 10 minates; After chilling, the product was collected onafilter and washed with methyl alcohol, It was purified by beingdissolved in hot pyridine, and adding methyl alcohol to the hotfiltrate. The yield o f product was crude, and 38% after two suchpurifications, The reddish crystals had a "melting point of 274-275 C.with decompositi'on, and they sensitized a photographicgelatinos'ilver-bromoiodide emulsion to about 630 mp with maximal.sensitivity about 530 m and about 580 m To a suspension of 0.54 g. (1mol.) of 5-chloro- 3-ethyl- 3-methyl 9methylmercapto-oxathiacarbocyanine iodide in 35 cc. of ethyl alcohol wasadded 0.16 g. (1 mol.+l00% excess) of sodium sulfide dissolved in 2 cc.of water, and the reaction 'mixture was heated at the refluxingtemperature for 10 minutes. After chilling, the prod-- not was collectedon a filter and washed with ethyl alcohol. The yield of product was 25%crude, and 12% after two recrystallizations from absolute ethyl alcohol.The brownish needles had a melting point of 22l-222 C. withdecomposition, and they sensitized a photographicgelatino=silver-broinoiodide emulsion to about aeolg Zidene] -3-methyl3- [3-methyZ-2fi3) 17811,- zothiazolylidenelthioacetone A mixture of 4.?g. (1 mol.) of 5-chloro-2-(2- methyl mercaptobutenyl)benzothiazoleetho-ptoluenesulfonate and 3&67 g. (1 mol.) of2-methylmercaptobenzothiazole metho-p-toluenesulfonate in 25 cc; ofpyridine were heated together at the refluxing temperature for 30minutes. The cool reaction mixture was stirred with ether and the wholechilled. The ether-pyridine layer was decanted, the sticky residue wasdissolved in hot methyl alcohol and the dye converted to the perchlorateby adding a hot aqueous solution of sodium perchlorate. After chilling,the aqueousalcohol layer was decanted and the residue was treated withseveral successive portions: of ethyl alcohol. The small residueremained sticky; it was dissolved in hot ethyl alcohol and treated withan aqueous solution of sodium sulfide at the refluxing temperature, for10 minutes. After chilling, the product was collected on a filter andwashed with ethyl alcohol. It was purified by dissolving in hotpyridine, and adding methyl alcohol to the hot filtrate. The yield ofproduct was 5% crude, and 3% after two such purifications. The redneedles had a melting point of 290 -291 C. with decomposition, and theysensitized a photographic gelatino-silver-bromoicdide emulsion to about630 mp with maxima sensitivity at about 520 m and about 575 m Example9.-Bis[3 ethyl 2(3) benzothiazolylidencl thioacetone To a suspension of0.30 g. (1 mol.) of 3,3'-diethyl-'9#ethylselenylthiacarbocyanine iodidein 20 cc. of ethyl alcohol, 0.08 g. (l mol.+100%) of sodium sulfidedissolved in 3 cc. of water was added, and the reaction mixture washeated at the refluxing temperature for 15 minutes. After chilling to 0C., the product was collected on a filter and washed with methylalcohol. The yield of the product was 100% crude, and after twopurifications (the crude product was dissolved in hot pyridine and 5volumes of methyl alcohol was added to the hot filtrate). The reddishcrystals had a blue reflex and melted at 29l-292 C. A mixedmelting pointof the dye of the above example and that of Example 1 was run, and themixture melted at 29l-292 C.

In a similar manner, other bis acetones can be prepared by replacing thealkylmercapto or alkylselenyl dy'es used in the above examples with anequivalent amount of one of the dyes represented by Formula 11 above.For example, by replacing the 9-methylmercapto dyes of Examples 1 to 7by a molecularly equivalent amount of 3,3-diethy1 9ethylselenylthiacarbocyanine perchlorate and the sodium sulfide orsodium selenide by a molecularly equivalent amount of sodium hydroxide,bis(3-ethyl-2(3) -benzothia'zo-.-

lylidene)acetone represented by the following can be obtained.Similarly, by replacing the sodium sulfide or sodium selenide inExamples 1 to 9 by a molecularly equivalent amount of sodium oxide(NazO) the corresponding bis acetones can be obtained, e. g., heating 1mol. of -chloro-3-ethyl-3-methyl-Q-methylmercaptooxathiacarbocyanineiodide with 1 mol. plus 100% excess of sodium oxide in the mannerdescribed in Example 7 gives 1-[5-chloro-3-ethyl-2(3)-benzothiazolylidene] 3-[3-methyl-2(3)-benzoxazolylidenelacetonerepresented by the formula:

If the 3,3-diethyl-Q-methylmercaptothiacarbocyanine iodide of Example 1is replaced by a molecularly equivalent amount of 3-ethyl-9-methylmercapto-3',4-trimethylenethiacarbocyanine perchlorate, 1-[3-ethyl-2(3) -benzothiazolylidene] 3 [3,4 trimethylene-2(3)-benzothiazolylidene]selenoacetone represented by the formula:

can be obtained. When a molecularly equivalent amount of sodiumhydrosulfide replaces the sodium selenide in Example 2, bis(3-ethyl-2(3)- benzothiazolylidene)thioacetone can be obtained. Othermetal sulfides, hydrosulfides, oxides, hy-

droxides, selenides and hydroselenides can likewise be advantageouslyused to produce our new bis-acetone compounds.

Our new bis acetone, bis thioaoetone and bis selenoacetone compounds areuseful as starting materials for the preparation of carbocyanine dyescontaining at the central position of the trimethine chain (the mesoposition) an oxy (-OR5), mercapto (SR5) or selenomercapto (--SeR5)substituent. Various compounds of the formula:

wherein X represents an anion and R5 represents an organic radical canbe added to the his acetone, bis thioacetone and bis selenoacetonecompounds, e, g., methyl iodide, ethyl iodide, n-propyl bromide, n-buty1chloride, n-butyl iodide, isobutyl bromide, n-decyl bromide, laurylbromide, cetylbromide, B-hydroxyethyl bromide, 'y-hYdIOX- ypropylbromide, [S-rnethoxyethyl bromide, ,B-ethoxyethyl bromide, bromoaceticacid, ii-bromopropionic acid, a-bromopropionic acid, ethyl bromoacetate,ethyl B-iodopropionate, 2-chloroquinoline, 2-ch1orobenzothiazole,-ohloroquinoline, 2- chloropyridine, methyl p-toluenesulfonate, ethylp-toluenesulionate, methyl benzenesulfonate, di-.

8 methyl sulfate, diethyl sulfate, 2,4-dinitrochloi'obenzene, etc.

The additions are advantageously efiected by heating the bis acetone,bis thioacetone or bis selenoacetone with the m5 compound at to C.Higher or lower temperatures can be used.

The following examples will serve to illustrate further the manner ofobtaining meso-substh tuted carbocyanine dyes in accordance with ourinvention.

Example 10.3,3-diethyl-Q-ethylselenylthiacarbocyanine iodide 0.89 g. (1mol.) of bis (3-ethyl-2(3) -benzothiazolylidene)selenoacetone and 2.00g. (1 mol.+ 400% excess) of ethyl p-toluenesulfonate were heatedtogether in an oil-bath at 120 C. for 6 minutes. The excess of ethylp-toluenesulfonate was removed with ether. The crude dye was dissolvedin methyl alcohol and the hot alcoholic solution was treated with a hotsolution of potassium iodide (3 g.) in water (30 00.). After chilling at0 0., the dye iodide was collected on a filter and washed with water.The dye was transferred to a beaker and stirred with hot acetone. Afterchilling at 0 C., the dye Was collected on a filter and washed withacetone. The yield of dye was 83% crude, and 58% after tworecrystallizations from methyl alcohol (45 cc. per gram of dye), Theblue and green crystals had a melting point of l78-179 C. withdecomposition, and they sensitized a photographicgelatino-silverbromoiodide emulsion to about 680 m with maximumsensitivity at about 640 m n.

In like manner, 3,3-diethyl-9-methy1selenylthiacarbocyanine iodide wasprepared by using 1.86 g. (1 mol.+400% excess) of methylp-toluenesulfonate in place of the ethyl p-toluenesulfonate. The yieldof dye iodide was 80% crude and 64% after two recrystallizations frommethyl alcohol (55 cc. per gram of dye). The beautiful green crystalshad a melting point of 162 C. with decomposition, and they sensitized aphotographic gelatino-silver-bromoiodide emulsion to about 665 m Example1 1 .-9-Carbethorymethylmercapto- 3,3-diethylthiacarbocyanine iodide s sSCHzCOOCzHs o=0H- t=oH-o N N 62115 Gi H5 \I r 0.99 g. (1 mol.) of bis(3-ethyl-2(3)-benzothiazolylidine)thioacetone and 1.67 g. (1 mol.+ 300%excess) of ethyl bromoacetate were heated together at the temperature ofthe steam bath for about 2 hours. The cake of crystals was broken up,ground under acetone, filtered and washed with acetone. The dye wasdissolved in methyl alcohol and the hot alcoholic solution was treatedwith a hot solution of aqueous potassium iodide. After chilling at 0 C.,the dye was collected on a filter and washed with water. The dye wastransferred to a beaker and stirred with hot acetone. After chilling at0 0., the dye was collected on a filter and washed with acetone. Theyield of dye was 85% crude and 52% after two recrystallizations frommethyl alcohol (50 cc. per gram of dye). The green needles had a meltingpoint of 1729-173 0. with decomposition, and they sensitized aphotographic gelatinosilver-bromoiodide emulsion to about 640 m In likemanner, 9-c-carboxyethylmercapto- 3,3-diethylthiacarbocyanine iodide wasprepared by heating 0.79 g. (1 mol.) of his (3ethyl-2(3)-benzothiazolylidene)thioacetone and 2.00 g. (1 mo1.+400% excess) ofc-iodopropionic acid together in an oil bath at 120 C. for 4 minutes.The yield ofdye was 96% crude and 71% after two recrystallizations frommethyl alcohol (160 cc. per gram of dye). The blue-green needles had amelting point of 246-247 C. with decomposition, and they sensitized aphotographic gelatinosilVer-bromoiodide emulsion to about 650 m 0.99 g.(1 mol.) of bis(3-ethyl-2(3) -benzothiazolylidene)thioacetone and 1.70g. (1 mol.+ 300% excess) of z-chlorobenzothiazole were heated togetherat the temperature of the steam bath for 4 hours. The cool reactionmixture was stirred with acetone, and the dye was collected on a filterand washed with acetone. The yield of twice-recrystallized dye (frommethyl alcohol, 125 cc. per gram of dye) was 11%. The dull purplishcrystals had a melting point of 252-254 C. with decomposition, and theysensitized a. photographic gelatino silver-bromoiodide emulsion to about615 In with maxima sensitivity at about 520 and 590 m The new bisacetone dyes (including the his thioacetone and his selenoacetone dyes)and the carbocyanine dyes obtained therefrom sensitize photographicsilver halide emulsions when incorporated therein.

In the preparation of photographic emulsions containing our new bisacetone dyes or carbocyanine dyes made therefrom, it is only necessaryto disperse the dyes in the emulsions. The methods of incorporating dyesin emulsions are simple well known to those skilled in the art It isconvenient to add the dyes from solutions in appropriate solvents.Methanol has proved satisfactory as a solvent for some of our new bisacetone dyes and for carbocyanine dyes made therefrom. A mixture ofpyridine and acetone can be used Where the solubility of the new bisacetone dyes in methanol is lower thandesired.

Sensitization by means of our new bis acetone dyes and carbocyanine dyesmade therefrom is, of course, directed primarily to the ordinarilyemployed gelatino-silver-halide developing-out emulsions. The dyes areadvantageously incorporated in the washed, finished emulsions andshould, of course, be uniformly distributed throughout the emulsions.

The concentration of our new bis acetone dyes and carbocyanine dyes madetherefrom in the emulsion can vary widely, i. e., from about 5 to aboutmgs. per liter of flowable emulsion. The concentration of the dye willvary according to the type of light-sensitive material in the emulsionand according to the eiiects desired. The suitable and most economicalconcentration for any given emulsion will be apparent to those skilledin the art upon making the ordinary tests and observations customarilyused in the art of emulsion making.

To prepare a gelatino-silver-halide emulsion sensitized with one of ournew bis acetone dyes or a carbccyanine dye made therefrom, the followingprocedure is satisfactory: A quantity of the dye is dissolved in methylalcohol or other suitable solvent and a volume of this solution (whichmay be diluted with water) containing from 5 to 100 mgs. of dye isslowly added to about 1000 cc. of a gelatino-silver-halide emulsion,with stirring. stirring is continued until the dye is uniormlydistributed throughout the emulsion. With most of our new bis acetonedyes, 10 to '20 mgs. of dye per liter of emulsion suffices to producethe maximum sensitizing efiect with the ordinary gelatino-silver-bromide(including bromiodide) emulsions. With fine-grain emulsions, whichinclude most of the ordinarily employed gelatino-silver-chlorideemulsions, somewhat larger concentrations of dye may be necessary tosecure the optimum sensitizing effect.

The above statements are only illustrative and are not to be understoodas limiting our invention in any sense, as it will be apparent that ournew bis acetone dyes and carbocyanine dyes made therefrom can beincorporated by other methods in many of the photographic silver halideemulsions customarily employed in the art. For instance, the dyes may beincorporated by bathing a plate or film upon which an emulsion has beencoated, in the solution of the dye, in an appropriate solvent. Bathingmethods, however, are not to be preferred ordinarily.

One method of preparing the alkylmercapto carbocyanine dyes, from whichour new bis acetones can be prepared, comprises condensing, in thepresence of a basic condensing agent, a cyclammonium quaternary saltrepresented by the following general formula:

n-Nlfon-on)., 1R:o=i -om1u wherein R, R2, R3, R4, Z, X and d have thedefinitions set forth above, with a cyclammonium alkyl quaternary saltrepresented by the following general formula:

Rl1 f= on-oH ,.I=os-m wherein R1, Z1, Z and n have the values set forthabove, and R6 represents an alkyl group, e. g. methyl, ethyl, n-butyl,benzyl, etc. groups, or an aryl group, e, g. phenyl, p-chlorophenyl,,B-naphthyl, etc. groups. Such a process is described in the copendingapplication of H. W. J. Cressman, Ser. No. 624,91,fi16d Oct. 26, 1945';As basic condensing agents we can use a tertiar amine (e. g. pyridine,triethylamine, dimethylaniline, tri-n-butylamine, etc.), alkali metalcarbonates (e; g. sodium or potassium carbonate, etc.), etc. Heatingaccelerates the condensations. While the copending application ofCressman relates to 11 condensations wherein R2 and R3 in the aboveformula represent hydrogen atoms, it is to be understood that ourinvention contemplates condensations wherein R2 and R3 each representseither a hydrogen atom or an alkyl group. Intermediates wherein R2 ofFormula Ia represents an alkyl group can be prepared by methodsdisclosed in U. S. Patents 2,369,646 and 2,369,657, dated Feb. 29, 1945.Intermediates wherein R2 and R3 of Formula Ia each represents an alkylgroup, and intermediates wherein R2 represents an alkyl group and R3represents a hydrogen atom are described in the copending application ofG. H. Keyes, Serial No. 620,161, filed Oct. 3, 1945, now U. S. Patent2,500,126, dated March 7, 1950. The intermediates of Formula Ia are, ingeneral, prepared by treating the thioketones described in U. S. Patents2,369,646 and 2,369,657, with an alkyl salt (e. g. methylp-toluenesulfonate, ethyl benzenesulfonate, etc.) e. g.

III

R-rf-Z6H=o1. 3;1%=o o112-R3 R X s z SR4 R-1 T=(oH-oH)d:=T1-o= :omm

wherein R, R2, R3, R4, Z, X and d have the values set forth above. Theintermediates represented by Formula III above can be prepared byreacting a compound selected from those represented by the followinggeneral formula:

IV X1 RITI =ZCHCH)a-1 CC=(BCHQR n-rf-(omomdlbzo-o-om-na wherein R, R2,R3, Z and d hav the values defined above, with a phosphorus oxyhalide,e. g. phosphorus oxychloride as described in U. S. Patent 2,231,659,dated Feb. 11, 1941. The compounds represented by Formula V can beprepared by reacting cyclammonium quaternary salts represented by thefollowing general formula:

wherein R, R2, Z, X and d have the values defined above, with an acylchlorid selected from those represented by the formula:

wherein R2 has the above designated value, in the presence of an acidbinding agent (e. g. pyridine, dimethylaniline, etc.) as described in U.S. Patent 2,112,139, dated Mar. 22, 1938. Many of the cyclammoniumquaternary salts represented by Formula VI above are known. Theheterocyclic bases themselves, from which the w ernary salts of FormulaVI can be prepared are also known for the most part. Several of the 2-methylbenzothiazole bases can be prepared by the method of Fries et al.,Ann. 4-07, 208 (1915), in which the appropriate thioacetylaniline isoxidized with alkalin potassium ferricyanide. Thusp-chlorothioacetanilide can be prepared by treating the correspondingacetylaniline with phosphorus pentasulfide. The acetylanilines can beprepar d by the action Of acetic anhydride or acetyl chloride on thecorresponding aniline compound. Several of the 2-methylbenzothiazolebases can also be prepared by reducing bis (0- nitrophenyDdisulfideswith zinc dust and acetic acid, acetylating the reduction mixture withacetic anhydride, and closing the ring by heating the resulting mixture.The bis (o-nitrophenyl) disulfides can be prepared from thecorresponding o-bromonitrobenzenes by heating the o-bromonitrobenzenewith sodium disulfide in methyl alcohol. Thus Z-bromo 4chloronitrobenzene give bis(5-chloro2-nitrophenyl) disulfide which, onreduction and acetylation of the reduction product and closing the ringby heating the re sulting mixture, gives 2-methyl-6-chlorobenzothiazole.2-methyl-5-phenylbenzothiazole can be prepared by reducingbis(3-nitro-4-biphenyl)- disulfide with zinc and acetic acid,acetylating the reduction product and closing the ring by heating theresulting mixture. (See the copending application of Gertrude Van Zandtand L. G. S. Brooker, Serial No. 711,816, filed November 22, 1946, nowPatent 2,515,913, July 18, 1950.) 2-methyl-4-phenylbenzothiazole can beprepared by oxidizing o-thioacetamidobiphenyl with an alkali metalferricyanide. (See the copending application of Gertrude Van Zandt andL, G. S. Brooker, Serial No. 709,414, filed November 13, 1946, now U. S.Patent 2,405,679, dated October 25, 1949.) Z-methylbenzoselenazole basescan be prepared by reducing bis(o-nitrophenyl) diselenides with zincdust and acetic acid, acetylating the reduction mixture with aceticanhydride, and closing the ring by heating the resulting mixture. Thebis(o-nitrophenyl) diselenides can be prepared from the correspondingo-bromonitrobenzenes by heating the 0-bromonitrobenzenes with sodiumdiselenide in methyl alcohol. See also Clark, J. Chem. Soc. (London)1928, 2313. Other 2-alkylcyclammonium bases can be prepared in a similarmanner by substituting other acylating agents for the correspondingacetyl derivatives used above. For example, Z-ethylbenzothiazol can beprepared by heating 2-aminothiopheno1 with propionyl chloride (Hofmann,Berichte, vol. 13, 21).

Another method for making the alkylmer -apto carbocyanine dyes, fromwhich our new bis acetones can be prepared, comprises condensing, in thepresence of a basic condensing agent (e. g. pyridine, dimethylaniline,quinoline, etc.), a cyclammonium quaternary salt selected from thoserepresented by Formula VI with a trithiocarbonate selected from thoserepresented by the following general formula:

wherein R4 has the definition designated above. Heat accelerates thereaction. This method yields symmetrical dyes, i. e. dyes wherein Z andZ1 in the above general formulas represent the atoms necessary tocomplete the same heterocyclic nucleus.

Still another method for preparing the alkylmercapto carbocyanine dyesfrom which our new bis acetones can be. prepared,.comprises condensing acyclammonium quaternary salt selected from those represented by thefollowing general formula:

VII SR4 wherein R1, R3, R4,.Z1, X and n have the values set forth above,with a cyclammonium quaternary salt selected from those represented byFormula VI above. The condensations are advantageously, effected in. thepresence of a basic condensing agent (0. g. pyridine, triethylamine,quinoline, dimethylam'line, etc.). Heat accelerates the reaction. Theintermediates represented by Formula VII above can be prepared bycondensing the corresponding dithioacetic acid with an alkyl salt (e. g.RiX) in the presence of an alcohol.

One method for preparing the alkylselenyl dyes, from which our bisacetones can be prepared, comprises condensing in the presence of abasic condensing agent (e, g. pyridine, triethylamine, quinoline,dimethylaniline, etc.), a cyclammonium quaternary salt selected fromthose represented by the following eneral formula:

wherein R, R2, R3, R4, Z, X and d have the values set forth above with.a cyclammonium quaternary salt selected from those represented by thefollowing general formula:

iii-640E011 "Lira,

wherein R1, Z, X and n have the values set forth above, and R7represents a halogen atom (e. g. chlorine) ora group, wherein R6 and Q1have the values set forth above. Heat accelerates the condensations. Theintermediates represented by Formula VIII above can be prepared in amanner similar to that illustrated by Formula Ia, except that thecorresponding selenium compounds are employed for the sulfur compoundsillustrated.

Some of the bis acetones of this invention exhibit interesting behaviortoward solutions of silver nitrate. For example, th his thioacetone ofExample 1 is turned. a bright bluish red upon the addition of a silvernitrate solution. Similar behavior is exhibited by the biasselenoacetone of Example 2, provided methyl alcohol. is added to preventprecipitation of the product. The bis acetone prepared in Example 2, i.e.

which is yellow in acetone, is not changed much by the addition ofdilute aqueous silver nitrate solution. The deeper colored productsformed .upon addition of a silver nitrate solution are probably silvercomplexes, e. g. that formed by the addition of a silver nitratesolutionto the his selenoacetone of Example 1, has the probableconstitution of the type:

Xa S

\ N N 12115 l zHs and XI) S S In this typ of resonance, Xa andb willclearly be more favored the greater the basieity of the heterocyclicring. The greater the resonance between the dipolar structures. of thetype of Xa Xb, the more the color of the compound will approach that ofa 9-substituted1 mercapto carbocyanine.

What we claim as our invention and desire to be secured by Letters.Patent of the United States is:

1. A bis acetone compound selected from those which are represented bythe following general formula:

wherein R and R1 each represents an alkyl group containing from 1 to 4carbon atoms, R2 and R3 each represents a member selected from the groupconsisting of a hydrogen atom and an alkyl group containing from 1 to 2carbon atoms, d and n each represents a positive integer .of from 1 to2, Q represents a member selected from the group consisting of an oxygenatom, a sulfur atom and a selenium atom, and Z and Z1 each representsthe non-metallic atoms necessary to complete a heterocyclic nucleuscontaining from 5 to 6 atoms in the heterocyclic ring.

2. A bis thioacetone compound selected from those represented by thefollowing general formula:

o=on-oon=o wherein R, represents a primary alkyl group of the formulaCmH2m+1 wherein m represents a positive integer of from 1. to 4 and Zrepresents the non-metallic atoms necessary to complete a heterocyclicnucleus of the benzothiazole series,

15 3. A bis thioacetone compound selected from those represented by thefollowing general formula:

wherein R. represents a primary alkyl group of the formula CmH2m+1wherein m represents a positive integer of from 1 to 4.

4. The bis thioacetone compound which is represented by the followingformula:

5. A bis selenoacetone compound selected from those represented by thefollowing general formula:

wherein R represents a primary alkyl group of the formula CmH2m+1wherein m represents a positive integer of from 1 to 4 and Z representsthe non-metallic atoms necessary to complete a heterocyclic nucleus ofthe benzothiazole series.

6. A bis selenoacetone compound selected from the group consisting ofthose represented by the following general formula:

wherein R represents a primary alkyl group of the formula CmH2m+1wherein m represents a positive integer of from 1 to 4.

7. The bis selenoacetone compound which is represented by the followingformula:

8. A bis acetone compound selected from those represented by thefollowing general formula:

/Z\ ,2 l R-N o=oH-corr=o N-R wherein R represents a primary alkyl groupof the formula CmH2m+1 wherein m represents a positive integer of from 1to 4 and Z represents the non-metallic atoms necessary to complete aheterocyclic nucleus of the benzothiazole series. 9. A bis acetonecompound selected from those represented by the following generalformula:

wherein R represents a primary alkyl group of the formula CmHZm-l-lwherein m represents a positive integer of from 1 to 4.

10. The bis acetone compound which is represented by the followingformula:

(52115 JzHs wherein R and R1 each represents an alkyl group of theformula CmH2m+l wherein m represents a positive integer of from 1 to 4.

13. The bis thioacetone compound which is represented by the followingformula:

14. The bis thioacetone compound which is represented by the followinggeneral formula:

wherein R and R1 each represents an alkyl group of the formula CmH2m+1wherein m represents a positive interger of from 1 to 4, R3 representsan alkyl group containing from 1 to 2 carbon atoms, Z represents thenon-metallic atoms necessary to complete a heterocyclic nucleus of thebenzoxazole series, and Z1 represents the non-metallic atoms necessaryto complete a heterocyclic nucleus of the benzothiazole series.

15. The bis thioacetone compound which is represented by the followinggeneral formula:

wherein R and R1 each represents an alkyl group of the formula CmH2m+1wherein m represents a positive integer of from 1 to 4.

16. The bis thioacetone compound which is represented by the followingformula:

17. A process for preparing bis acetone compounds comprising heating acompound selected from those represented by the following generalformula:

wherein R and R1 each represents a primary alkyl group of the formulaCmH2m+1 wherein m is a positive integer from 1 to R2 and R3 eachrepresents a member selected from the group consisting of a hydrogenatom, a methyl group and an ethyl group, R4 represents a primary alkylgroup of the formula CqH2q+1 wherein q represents a positive integerfrom 1 to 20, X represents naphthothiazole series, the selenazoleseries, the

benzoselenazole series, the thlazoline series, the 3,3-dialkylindolenineseries, the quinoline series and the pyridine series, with an aqueoussolution of a member selected from the group consisting of metal oxides,metal hydroxides, metal sulfides, 4

metal hydrosulfides, metal selenides and metal hydroselenides.

18. A process for preparing his acetones com,- prising heating acompound selected from those represented by the following generalformula:

wherein R and R1 each represents a primary alkyl group of the formulaCmH2m+1 wherein m represents a positive integer of from 1 to 4, R4

wherein R and R1 each represents a primary alkyl group of the formulaC'mHzm rl wherein m represents a positive integer of from 1 to 4, R4represents a primary alkyl group of the formula CqH2q+1 wherein qrepresents a positive integer of from 1 to 20, X represents an anion,and. Z and Z1 each represents the non-metallic atoms necessary tocomplete a heterocyclic nucleus containing from 5 to 6 atoms in theheterocyclic ring, with a metal selem'de.

20. A process for preparing his acetones comprising heating a compoundselected from those represented by the following general formula:

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Name Date Reister June 1 1940 Number

1. A BIS ACETONE COMPOUND SELECTED FROM THOSE WHICH ARE REPRESENTED BYTHE FOLLOWING GENERAL FORMULA: